Synthesis of N-acryloxysuccinimide copolymers by RAFT polymerization, as reactive building blocks with full control of composition and molecular weights

Favier, Arnaud; D’Agosto, Franck; Charreyre, Marie‐Thérèse; Pichot, Christian

doi:10.1016/j.polymer.2004.09.042

Cited by 105 publications

(134 citation statements)

References 67 publications

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“…1). [46] S-1-dodecyl-S 0 -(a,a 0 -dimethyl-a 00 -acetic acid)trithiocarbonate (DDMAT) was selected as the chain transfer agent (CTA), due to its facile preparation [47] linking with diamino crosslinkers, while NAM imparted hydrophilicity for the entire copolymer segment. Many parameters can contribute to the size and morphology of block copolymer assemblies.…”

Section: Resultsmentioning

confidence: 99%

Facile Formation of Uniform Shell‐Crosslinked Nanoparticles with Built‐in Functionalities from N‐Hydroxysuccinimide‐Activated Amphiphilic Block Copolymers

Li¹,

Akiba

Harrisson

et al. 2008

Adv Funct Materials

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An amphiphilic block copolymer, poly(methylacrylate)82‐block‐poly(N‐(acryloyloxy)succinimide0.29‐co‐(N‐acryloylmorpholine)0.71)155 (PMA82‐b‐P(NAS0.29‐co‐NAM0.71)155), was synthesized by reversible addition‐fragmentation chain transfer (RAFT) polymerization and then was supramolecularly assembled into micelles in aqueous solution, followed by chemical crosslinking throughout the shell region upon the introduction of 2,2′‐(ethylenedioxy)‐bis(ethylamine) as a crosslinker to afford well‐defined shell crosslinked nanoparticles (SCKs). The number‐averaged hydrodynamic diameters of the micelles and SCKs were (17 ± 4) nm and (16 ± 3) nm, respectively, by dynamic light scattering (DLS), and (15 ± 2) nm and (13 ± 2) nm, respectively, by transmission electron microscopy (TEM). In an attempt to narrow the particle size distributions, the dodecyl trithiocarbonate chain end of the block copolymer was replaced by a 2‐cyanoisopropyl moiety. Each nanoparticle system was characterized by DLS, electrophoretic light scattering (ELS), TEM, and small‐angle X‐ray scattering (SAXS). SAXS was of particular importance, as it provided definitive observation and quantification of shell contraction and densification upon shell crosslinking. The direct incorporation of NAS into the block copolymers during their preparation allowed for unique crosslinking chemistry to proceed with added diamino crosslinkers. The primary advantages of this system include the ability to conduct in situ synthesis of SCKs that are crosslinked directly and derivatized easily by adding nucleophilic ligands before, during, or after the crosslinking.

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Section: Resultsmentioning

confidence: 99%

Facile Formation of Uniform Shell‐Crosslinked Nanoparticles with Built‐in Functionalities from N‐Hydroxysuccinimide‐Activated Amphiphilic Block Copolymers

Li¹,

Akiba

Harrisson

et al. 2008

Adv Funct Materials

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“…39 In contrast, the copolymerization of NHSA with N,N-diethyl acrylamide was successful under RAFT conditions. 40 A good control of molecular weight (5000 g/mol \ M n \ 130,000 g/mol), narrow molecular weight distributions (M w /M n \ 1.1), and reasonable yields of up to 70% were achieved. In similar experiments, Kane and coworkers 41 reported on the RAFT copolymerization of NHSMA with N-(2-hydroxypropyl)methacrylamide in a wide range of molecular weights (M n ¼ 3000-50,000 g/mol) with narrow molecular weight distributions (M w /M n ¼ 1.1-1.3), which may be used in polymeric therapeutics.…”

Section: Raft Polymerizationmentioning

confidence: 95%

Synthesis of well‐defined polymeric activated esters

Théato

2008

J. Polym. Sci. A Polym. Chem.

271

258

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Monomers bearing an activated ester group can be polymerized under various controlled polymerization techniques, such as ATRP, NMP, RAFT polymerization, or ROMP. Combining the functionalization of polymers via polymeric activated esters with these controlled polymerization techniques generate possibilities to realize highly functionalized polymer architectures. Within this highlight two different research areas of activated esters in polymer science will be discussed: (i) the preparation of defined reactive polymer architectures by controlled polymerization techniques and (ii) the preparation of defined reactive thin films. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6677–6687, 2008

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“…A drawback of polyNAS and polyNMAS is that they are only soluble in DMF and DMSO. The solubility of active-ester-based polymer precursors can be improved by copolymerization [4] or by replacing the NHS ester group with other activating groups, [5] such as 2,4,5-trichlorophenol ester, [5] endo-N-hydroxy-5-norbornene-2,3-dicarboxyimide, [5] or pentafluorophenol ester groups, as shown by ThØato and co-workers. [6,7] Another interesting active ester monomer is diNAS, which is a bis(active ester) monomer that was isolated as a byproduct from the synthesis of NAS.…”

Section: Modification Of Polymeric Active Estersmentioning

confidence: 96%

“…[11] Smith et al observed that the extent of grafting of an RGD peptide onto polyNAS decreased with increasing pH value and temperature owing to promotion of hydrolysis. [11] Cline and Hanna have noted that the reactivity of various amines towards aminolysis of p-nitrobenzoyl-Nhydroxysuccinimide in anhydrous dioxane correlated strongly with the basicity of the amino group, though steric hindrance within the investigated set of amines caused certain deviations [11,16] diNAS [8] NAS [18] NMAS [9,15,19] NAS [20] NSVB [20] NAS [4,13] NMAS [21,22] NSVB [23] NNHS [24] PFA [6] PFMA [6] PFVB [25] PFMA [26] NPF [7] NPA [27] NPMA [28] NPA [29] NPMA [30] MAPTT [10] 3 MA [17] MA [31] MA [32] MVI [17,33] VI [33] TMI [34] VDM [35,36] VDM [37] VDM [38] VPDMO [38] IDMO [38] GMA [39] GMA [40] 4-ES [41] GMA [42] GA [43] GMA …”

Section: Reviews 50mentioning

confidence: 99%

“…Imines are hydrolytically labile and must be reduced, a process referred to as reductive alkylation, to improve their stability. This reduction is generally accomplished using NaBH 4 or NaCNBH 3 , which react optimally at basic or neutral pH values, respectively. [92] Oximes and hydrazones are hydrolytically stable between pH 2-7 and 5-7, respectively, but they decompose rapidly above pH 9.…”

Section: Modification Of Polymers Bearing Aldehydes and Ketonesmentioning

confidence: 99%

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Synthesis of Functional Polymers by Post‐Polymerization Modification

2008

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Post-polymerization modification is based on the direct polymerization or copolymerization of monomers bearing chemoselective handles that are inert towards the polymerization conditions but can be quantitatively converted in a subsequent step into a broad range of other functional groups. The success of this method is based on the excellent conversions achievable under mild conditions, the excellent functional-group tolerance, and the orthogonality of the post-polymerization modification reactions. This Review surveys different classes of reactive polymer precursors bearing chemoselective handles and discusses issues related to the preparation of these reactive polymers by direct polymerization of appropriately functionalized monomers as well as the post-polymerization modification of these precursors into functional polymers.

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Synthesis of N-acryloxysuccinimide copolymers by RAFT polymerization, as reactive building blocks with full control of composition and molecular weights

Cited by 105 publications

References 67 publications

Facile Formation of Uniform Shell‐Crosslinked Nanoparticles with Built‐in Functionalities from N‐Hydroxysuccinimide‐Activated Amphiphilic Block Copolymers

Facile Formation of Uniform Shell‐Crosslinked Nanoparticles with Built‐in Functionalities from N‐Hydroxysuccinimide‐Activated Amphiphilic Block Copolymers

Synthesis of well‐defined polymeric activated esters

Synthesis of Functional Polymers by Post‐Polymerization Modification

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